JP3160051B2 - Pickling accelerator, pickling liquid composition containing pickling accelerator, and method for promoting pickling of metal using the same - Google Patents
Pickling accelerator, pickling liquid composition containing pickling accelerator, and method for promoting pickling of metal using the sameInfo
- Publication number
- JP3160051B2 JP3160051B2 JP05522392A JP5522392A JP3160051B2 JP 3160051 B2 JP3160051 B2 JP 3160051B2 JP 05522392 A JP05522392 A JP 05522392A JP 5522392 A JP5522392 A JP 5522392A JP 3160051 B2 JP3160051 B2 JP 3160051B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- pickling
- accelerator
- solution
- inorganic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
- C23G1/065—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors sulfur-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、金属の表面に付着して
いる酸化物皮膜（錆、熱延ミルスケール等）および熱交
換器の表面に付着するスケール（金属酸化物と硬度成分
の混合物）の除去の際の酸洗液に添加する酸洗促進剤お
よび酸洗促進剤を含んだ酸洗液組成物ならびにこれらを
用いる金属の酸洗促進方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxide film (rust, hot-rolled mill scale, etc.) adhering to a metal surface and a scale (metal oxide and hardness component mixture) adhering to a heat exchanger surface. The present invention relates to a pickling accelerator to be added to the pickling solution at the time of the removal, a pickling solution composition containing the pickling accelerator, and a method for accelerating pickling of metals using the same.
【０００２】[0002]
【従来の技術】一般に金属の熱延材料（熱延鋼板など）
や熱処理を施した金属材料表面には、酸化物皮膜（ミル
スケールなど）が付着しており、後工程（冷延、メッキ
工程など）に供するためにこの酸化物皮膜を除去する必
要がある。2. Description of the Related Art Generally, hot-rolled metal materials (hot-rolled steel sheets, etc.)
An oxide film (such as a mill scale) adheres to the surface of the metal material that has been subjected to heat treatment or heat treatment, and it is necessary to remove the oxide film in order to provide it to a subsequent step (such as a cold rolling or plating step).
【０００３】また、発電プラント、化学プラントなどの
ボイラーや熱交換器には、金属酸化物を主体としその他
硬度成分を含んだスケールが、プラントの稼働とともに
生成する。スケールが金属表面に付着生成するとプラン
トの熱効率を悪化させたり伝熱管の異常加熱を引き起こ
し危険であるためスケールを除去する必要がある。[0003] In a boiler or a heat exchanger of a power plant, a chemical plant, or the like, a scale mainly composed of a metal oxide and containing other hardness components is generated with the operation of the plant. If the scale adheres to the metal surface, the heat efficiency of the plant is deteriorated or the heat transfer tube is abnormally heated, which is dangerous, so it is necessary to remove the scale.
【０００４】これら金属の表面に付着している酸化物皮
膜および熱交換器表面に付着しているスケールの除去に
は、酸、たとえば、硫酸、塩酸、リン酸、スルファミン
酸、硝酸、フッ酸、シュウ酸、クエン酸のような無機酸
または有機酸およびこれらの混酸等の水溶液による洗
浄、いわゆる酸洗が行われている。[0004] To remove the oxide film adhering to the surface of these metals and the scale adhering to the surface of the heat exchanger, an acid such as sulfuric acid, hydrochloric acid, phosphoric acid, sulfamic acid, nitric acid, hydrofluoric acid, or the like is used. BACKGROUND ART Washing with an aqueous solution of an inorganic acid or an organic acid such as oxalic acid or citric acid and a mixed acid thereof, that is, so-called pickling is performed.
【０００５】なお、これらの酸は、酸洗時において酸化
物皮膜やスケールを溶解するのみならず金属素地も同時
に溶解するため、従来から素地腐食の防止のために腐食
抑制剤が使用されている。[0005] These acids not only dissolve oxide films and scales during pickling, but also dissolve metal bases at the same time. Corrosion inhibitors have conventionally been used to prevent base corrosion. .
【０００６】酸洗において、強固に付着した酸化物皮膜
は、除去しがたく、これを完全に除去するには、かなり
長時間の酸洗時間が必要である。また、母材保護のため
使用されている腐食抑制剤の多くは、酸洗速度を遅らせ
るという欠点を有している。このため、さらに長時間の
酸洗時間が必要となり作業能率の低下が避けられないの
が実状である。[0006] In pickling, the oxide film firmly adhered is difficult to remove, and it takes a considerably long pickling time to completely remove it. Further, many of the corrosion inhibitors used for protecting the base material have a disadvantage that the pickling rate is reduced. For this reason, a longer time for pickling is required, and a reduction in work efficiency is inevitable.
【０００７】このため、腐食抑制剤の性能低下が起きな
い範囲内で酸濃度を高めたり酸洗液の温度を高めたりし
て酸化物皮膜を除去する時間を短縮する方法で対処して
いるのが実状である。For this reason, a method of reducing the time for removing the oxide film by increasing the acid concentration or increasing the temperature of the pickling solution within a range in which the performance of the corrosion inhibitor does not deteriorate is dealt with. Is the actual situation.
【０００８】したがって、母材の腐食を抑えながら酸洗
を促進し、酸洗に要する時間を短縮することは工業的に
重要であり強い要請のあるところである。[0008] Therefore, it is industrially important and strongly demanded to promote pickling while suppressing corrosion of the base material and to reduce the time required for pickling.
【０００９】従来、これらの問題点の解決にあたって界
面活性剤を添加する方法（特開昭５７−１９８２７
３）、酸化剤と腐食抑制剤を添加する方法（特開昭６３
−２０３７８０）、あるいは還元剤を添加する方法（特
開昭４７−３４１２２）などが提案されている。Conventionally, in order to solve these problems, a method of adding a surfactant (JP-A-57-19827).
3), a method of adding an oxidizing agent and a corrosion inhibitor (JP-A-63
207780) or a method of adding a reducing agent (Japanese Patent Laid-Open No. 47-34122).
【００１０】[0010]
【発明が解決しようとする課題】しかしながら、上記従
来技術では、充分な促進効果が発揮されない、酸洗作業
中に有毒ガスを発生し作業環境を悪化する、腐食抑制剤
の素地腐食防止効果に悪影響を与えるなどの問題点があ
る。このため上記の酸洗促進剤およびこれを用いた酸洗
促進方法は使用されることがほとんどないのが実状であ
る。However, in the above-mentioned prior art, a sufficient accelerating effect is not exhibited, a toxic gas is generated during the pickling operation, and the working environment is deteriorated. There are problems such as giving. Therefore, the above-mentioned pickling accelerator and the method of accelerating pickling using the same are rarely used.
【００１１】たとえば、特開昭５７−１９８２７３号公
報には、含フッ素系界面活性剤および炭化水素系界面活
性剤から成る酸洗促進剤が記載されているが充分な促進
効果が認められない。また、特開昭６３−２０３７８０
号公報の酸化剤と腐食抑制剤を添加する方法では、鉄の
溶解反応を促進し電気化学的作用により金属の表面に付
着している酸化物皮膜の溶解を促進するものであるが腐
食抑制剤を添加していても酸化剤添加によって金属素地
の腐食の増加は避けられない。特開昭４７−３４１２２
号公報には、還元性を有する無機または有機化合物を添
加する方法が記載されているが、アスコルビン酸、ヒド
ラジンなど有機還元剤では、充分な促進効果が認められ
ない。亜硫酸塩、チオ硫酸塩などの無機還元剤では、酸
化物皮膜の溶解促進作用があるものの酸洗液にこれらを
添加するときおよび酸洗中に、きわめて有毒な亜硫酸ガ
スや硫化水素ガスを発生し作業環境維持の立場からして
好ましいものではない。さらに、腐食抑制剤の素地腐食
の防止効果に悪影響を与え腐食量の増大をまねくという
問題点がある。For example, Japanese Patent Application Laid-Open No. 57-198273 describes a pickling accelerator comprising a fluorine-containing surfactant and a hydrocarbon surfactant, but does not show a sufficient accelerating effect. Also, JP-A-63-203780
In the method of adding an oxidizing agent and a corrosion inhibitor disclosed in Japanese Patent Application Laid-Open No. H11-284, the dissolution reaction of iron is promoted and the dissolution of the oxide film adhered to the surface of the metal is promoted by an electrochemical action. However, the addition of the oxidizing agent inevitably increases the corrosion of the metal substrate. JP-A-47-34122
In Japanese Patent Application Laid-Open Publication No. H08-157, a method of adding a reducing inorganic or organic compound is described, but an organic reducing agent such as ascorbic acid or hydrazine does not show a sufficient accelerating effect. Inorganic reducing agents such as sulfites and thiosulfates have the effect of accelerating the dissolution of oxide films.However, when they are added to pickling solutions and during pickling, extremely toxic sulfurous acid gas and hydrogen sulfide gas are generated. It is not preferable from the standpoint of maintaining the working environment. Furthermore, there is a problem that the corrosion inhibitor has an adverse effect on the effect of preventing corrosion of the substrate and leads to an increase in the amount of corrosion.
【００１２】本発明の目的は、上記の従来技術の問題点
である酸洗時において有害ガスを発生することなく、ま
た、腐食抑制剤の素地腐食の防止効果に悪影響を与えず
に金属表面に付着している酸化物皮膜やスケールの除去
速度を促進する酸洗促進剤および酸洗促進剤を含む酸洗
液組成物ならびにこれを用いる酸洗促進方法を提供する
ことにある。[0012] An object of the present invention is to produce a harmful gas at the time of pickling, which is a problem of the above-mentioned prior art, and to prevent a corrosion inhibitor from exerting an adverse effect on the effect of preventing body corrosion on a metal surface. It is an object of the present invention to provide a pickling accelerator which accelerates the removal rate of an attached oxide film and scale, a pickling liquid composition containing the pickling accelerator, and a pickling accelerating method using the same.
【００１３】[0013]
【課題を解決するための手段】本発明は、金属の酸洗工
程において、下記の化５で表される化合物の少なくとも
１種を無機酸および／または有機酸の水溶液に添加する
ことによって金属の酸洗速度を促進することを特徴とす
る酸洗促進剤である。According to the present invention, in a pickling step of a metal, at least one of the compounds represented by the following formula (5) is added to an aqueous solution of an inorganic acid and / or an organic acid to thereby remove the metal. It is a pickling accelerator characterized by accelerating the pickling speed.
【００１４】[0014]
【化５】 ＨＳＲ1−ＣＯＯ−Ｒ2−ＯＯＣ−Ｒ3ＳＨ Ｒ1，Ｒ2，Ｒ3 は、炭素１〜６のアルキル基を示し、そ
れぞれ同一であってもよく異なっていてもよい。Embedded image HSR 1 —COO—R 2 —OOC—R 3 SH R 1 , R 2 and R 3 each represent an alkyl group having 1 to 6 carbon atoms, and may be the same or different.
【００１５】また本発明は、エチレングリコールジチオ
グリコレートもしくは１，４−ブタンジオールジチオプ
ロピオネートまたはこれらの混合物を無機酸および／ま
たは有機酸の水溶液に添加することによって金属の酸洗
速度を促進することを特徴する。[0015] The present invention also enhances the pickling rate of metals by adding ethylene glycol dithioglycolate or 1,4-butanediol dithiopropionate or a mixture thereof to an aqueous solution of an inorganic acid and / or an organic acid. It is characterized by doing.
【００１６】また本発明は、無機酸および／または有機
酸の少なくとも１種の水溶液から成り、酸の含有量が１
〜５０％、下記の化６で表される化合物の少なくとも１
種の含有量が０．００１％以上であることを特徴とする
酸洗促進剤を含んだ酸洗液組成物である。Further, the present invention comprises at least one aqueous solution of an inorganic acid and / or an organic acid, wherein the acid content is 1%.
~ 50%, at least one of the compounds represented by the following Chemical Formula 6
A pickling liquid composition containing a pickling accelerator characterized by having a seed content of 0.001% or more.
【００１７】[0017]
【化６】 ＨＳＲ1−ＣＯＯ−Ｒ2−ＯＯＣ−Ｒ3ＳＨ Ｒ1，Ｒ2，Ｒ3 は、炭素数１〜６のアルキル基を示し、
それぞれ同一であってもよく異なっていてもよい。Embedded image HSR 1 —COO—R 2 —OOC—R 3 SH R 1 , R 2 and R 3 each represent an alkyl group having 1 to 6 carbon atoms;
Each may be the same or different.
【００１８】また本発明は、スルファミン酸および／ま
たは有機酸の少なくとも１種から成る酸の含有量が９
９．９９％未満と、下記の化７で表される化合物の少な
くとも１種の含有量が０．０１％以上であることを特徴
とする酸洗促進剤を含んだ酸洗液組成物である。Further, according to the present invention, an acid containing at least one of sulfamic acid and / or an organic acid has a content of 9%.
A pickling liquid composition containing a pickling accelerator, wherein the content of at least one of the compounds represented by the following Chemical Formula 7 is less than 9.99% and not less than 0.01%: .
【００１９】[0019]
【化７】 ＨＳＲ1−ＣＯＯ−Ｒ2−ＯＯＣ−Ｒ3ＳＨ Ｒ1，Ｒ2，Ｒ3 は、炭素数１〜６のアルキル基を示し、
それぞれ同一であってもよく異なっていてもよい。Embedded image HSR 1 —COO—R 2 —OOC—R 3 SH R 1 , R 2 and R 3 each represent an alkyl group having 1 to 6 carbon atoms;
Each may be the same or different.
【００２０】また本発明は、無機酸が硫酸、塩酸、リン
酸、スルファミン酸、フッ酸または硝酸であり、有機酸
が酢酸、シュウ酸、クエン酸、ギ酸、酒石酸、リンゴ
酸、ヒドロキシ酸またはグルコン酸であることを特徴と
する。In the present invention, the inorganic acid is sulfuric acid, hydrochloric acid, phosphoric acid, sulfamic acid, hydrofluoric acid or nitric acid, and the organic acid is acetic acid, oxalic acid, citric acid, formic acid, tartaric acid, malic acid, hydroxy acid or gluconic acid. It is an acid.
【００２１】また本発明は、無機酸および／または有機
酸の水溶液から成る酸洗液１ｌに、下記の化８で表され
る化合物の少なくとも１種類を１０ｍｇ以上添加した液
を用いることを特徴とする金属の酸洗促進方法である。Further, the present invention is characterized in that a solution obtained by adding at least one kind of the compound represented by the following formula (10 mg) to 1 liter of an pickling solution comprising an aqueous solution of an inorganic acid and / or an organic acid is used. This is a method for accelerating the pickling of metals to be washed.
【００２２】[0022]
【化８】 ＨＳＲ1−ＣＯＯ−Ｒ2−ＯＯＣ−Ｒ3ＳＨ Ｒ1，Ｒ2，Ｒ3 は、炭素数１〜６のアルキル基を示し、
それぞれ同一であってもよく異なっていてもよい。Embedded image HSR 1 —COO—R 2 —OOC—R 3 SH R 1 , R 2 and R 3 each represent an alkyl group having 1 to 6 carbon atoms;
Each may be the same or different.
【００２３】また本発明は、無機酸および／または有機
酸の水溶液から成る酸洗液１ｌに、前記化１で表される
化合物の少なくとも１種類を５０ｍｇ以上４，０００ｍ
ｇ以下添加した液を用いることを特徴とする。The present invention also relates to a pickling solution comprising an aqueous solution of an inorganic acid and / or an organic acid, wherein at least one kind of the compound represented by the formula (1) is added in an amount of 50 mg to 4,000 m
It is characterized by using a liquid added in an amount of up to g.
【００２４】また本発明は、無機酸が硫酸、塩酸、リン
酸、スルファミン酸、フッ酸または硝酸であり、有機酸
が酢酸、シュウ酸、クエン酸、ギ酸、酒石酸、リンゴ
酸、ヒドロキシ酸またはグルコン酸であることを特徴と
する。In the present invention, the inorganic acid is sulfuric acid, hydrochloric acid, phosphoric acid, sulfamic acid, hydrofluoric acid or nitric acid, and the organic acid is acetic acid, oxalic acid, citric acid, formic acid, tartaric acid, malic acid, hydroxy acid or gluconic acid. It is an acid.
【００２５】また本発明は、無機酸および／または有機
酸の水溶液から成る酸洗液１ｌに、前記化１で表される
化合物の少なくとも１種類を１０ｍｇ以上添加した液を
用いることを特徴とする。Further, the present invention is characterized in that a solution obtained by adding at least 10 mg of at least one kind of the compound represented by the above formula (1) to 1 liter of an acid washing solution comprising an aqueous solution of an inorganic acid and / or an organic acid is used. .
【００２６】[0026]
【作用】本発明に従えば、次の化９で表される化合物の
少なくとも１種を、金属の酸洗液である無機酸および／
または有機酸の水溶液に添加することによって、有毒ガ
スを発生せずに、また腐食抑制剤による金属の素地腐食
防止効果に悪影響を与えずにその酸洗速度を促進するこ
とである。According to the present invention, at least one kind of the compound represented by the following chemical formula (9) is added to an inorganic acid which is a pickling solution of metal and / or
Another object of the present invention is to increase the pickling rate of an organic acid by adding it to an aqueous solution of an organic acid without generating a toxic gas and without adversely affecting the effect of the corrosion inhibitor on the prevention of metal base corrosion.
【００２７】[0027]
【化９】 ＨＳＲ1−ＣＯＯ−Ｒ2−ＯＯＣ−Ｒ3ＳＨ Ｒ1，Ｒ2，Ｒ3 は、炭素数１〜６のアルキル基を示し、
それぞれ同一であってもよく異なっていてもよい。Embedded image HSR 1 —COO—R 2 —OOC—R 3 SH R 1 , R 2 and R 3 each represent an alkyl group having 1 to 6 carbon atoms;
Each may be the same or different.
【００２８】特にエチレングリコールジチオグリコレー
トもしくは１，４−ブタンジオールジチオプロピオネー
トまたはこれらの混合物が好ましい。さらに好ましい化
合物として、入手のし易いエチレングリコールジチオグ
リコレートがある。Particularly, ethylene glycol dithioglycolate or 1,4-butanediol dithiopropionate or a mixture thereof is preferred. More preferred compounds include readily available ethylene glycol dithioglycolate.
【００２９】また本発明の酸洗促進剤の添加量は、酸洗
液１ｌに対し、１０ｍｇ以上、好ましくは５０ｍｇ以
上、４，０００ｍｇ以下である。添加量が１０ｍｇ／ｌ
未満では、酸洗促進剤の作用が認められない。特に、添
加量が５０ｍｇ／ｌ以上で顕著な酸洗促進効果を示し、
４，０００ｍｇ／ｌを超えてもその作用はほとんど増加
しない。The addition amount of the pickling accelerator of the present invention is 10 mg or more, preferably 50 mg or more and 4,000 mg or less per liter of the pickling solution. Addition amount is 10mg / l
If it is less than 3, no action of the pickling accelerator is observed. In particular, when the added amount is 50 mg / l or more, a remarkable pickling accelerating effect is exhibited,
Even if it exceeds 4,000 mg / l, the effect hardly increases.
【００３０】また本発明の酸洗促進剤は、使用に際して
酸洗液に添加してもよく、また予め酸洗原液に添加して
酸洗液組成物とし、酸洗時にそのままでまたはこれを水
で希釈して用いることもできる。この場合酸洗原液とし
て、硫酸、塩酸、リン酸、フッ酸または硝酸もしくはこ
れらの混酸、これらと有機酸の混酸を用いるときは、酸
の含有量を１〜５０％とすることが好ましい。これは、
これらの酸の濃度が５０％を超えると、本発明の酸洗促
進剤の一部が分解するおそれがあるためである。酸洗原
液がスルファミン酸や、酢酸、シュウ酸、クエン酸、ギ
酸、酒石酸、リンゴ酸、ヒドロキシ酢酸またはグルコン
酸などの有機酸であるときは、本発明の酸洗促進剤は安
定であり、上記のように分解する恐れがないため、９
９．９９％未満の酸洗原液に本発明の酸洗促進剤０．０
１％以上添加したものを酸洗液組成物とすることができ
る。The pickling accelerator of the present invention may be added to a pickling solution at the time of use, or may be added in advance to an undiluted solution for pickling to form a pickling solution composition. Can be used after dilution. In this case, when sulfuric acid, hydrochloric acid, phosphoric acid, hydrofluoric acid or nitric acid, or a mixed acid thereof, or a mixed acid of these and an organic acid is used as the undiluted solution, the acid content is preferably 1 to 50%. this is,
If the concentration of these acids exceeds 50%, part of the pickling accelerator of the present invention may be decomposed. When the pickling stock solution is an organic acid such as sulfamic acid, acetic acid, oxalic acid, citric acid, formic acid, tartaric acid, malic acid, hydroxyacetic acid or gluconic acid, the pickling accelerator of the present invention is stable. Since there is no risk of decomposition like
The pickling accelerator 0.0
What added 1% or more can be set as a pickling liquid composition.
【００３１】酸洗促進剤を含んだ酸洗液組成物は、その
まままたはこれを水で希釈して用いることもできるし、
また、従来からある酸洗液にこれを混ぜ、水で濃度調整
して使用することもできる。The pickling solution composition containing a pickling accelerator can be used as it is or after dilution with water.
Further, this can be mixed with a conventional pickling solution, and the concentration can be adjusted with water for use.
【００３２】また、本発明の酸洗促進剤およびこれを含
んだ酸洗液組成物は、金属一般の酸洗に用いて、顕著な
酸洗促進作用を示すが、その対象金属として、鉄、炭素
鋼、ステンレスなどの特殊鋼、銅、真ちゅうなどの銅合
金を上げることができる。The pickling accelerator of the present invention and the pickling solution composition containing the same have a remarkable pickling accelerating effect when used for pickling metals in general. Special steels such as carbon steel and stainless steel, and copper alloys such as copper and brass can be raised.
【００３３】また、本発明の酸洗促進剤およびこれを含
んだ酸洗液組成物は、従来から使用されている腐食抑制
剤の腐食抑制作用に悪影響を与えずに酸洗促進作用を示
すため腐食抑制剤と併用し母材の腐食を抑制することが
望ましい。Further, the pickling accelerator of the present invention and the pickling liquid composition containing the same show the pickling accelerating action without adversely affecting the corrosion inhibiting action of the conventionally used corrosion inhibitor. It is desirable to use a corrosion inhibitor in combination to suppress the corrosion of the base material.
【００３４】さらに、酸洗液との混合をよくするために
界面活性剤と併用してもよい。これらの腐食抑制剤や界
面活性剤は、予め本発明の酸洗促進剤と混合しておいて
もよく、別々に添加してもよい。Further, it may be used in combination with a surfactant to improve the mixing with the pickling solution. These corrosion inhibitors and surfactants may be mixed in advance with the pickling accelerator of the present invention, or may be added separately.
【００３５】酸洗促進剤およびこれを含んだ酸洗液組成
物についてその作用を説明したが、本発明の作用はこれ
らを用いた金属の酸洗促進方法についても同様である。The action of the pickling accelerator and the pickling liquid composition containing the same has been described, but the action of the present invention is the same for the method of accelerating the pickling of metals using these.
【００３６】[0036]
実施例１〜３ １ｌ中に硫酸１００ｇと第１鉄イオン５０ｇと腐食抑制
剤イビットＮｏ．Ｓ６００Ａ（朝日化学工業株式会社
製）１ｇとを含む酸洗液に、本発明の酸洗促進剤を２ｇ
添加し、この液を６０℃まで加温した後、黒皮付きの熱
間圧延鋼板（ＪＩＳ Ｇ ３１３１）を浸漬し、表面の
黒皮、錆の除去に要する時間を測定した。その結果を表
１に示す。Examples 1 to 3 100 g of sulfuric acid, 50 g of ferrous ion and corrosion inhibitor Ibit No. 2 g of the pickling accelerator of the present invention in a pickling solution containing 1 g of S600A (manufactured by Asahi Chemical Industry Co., Ltd.).
After the solution was heated to 60 ° C., a hot-rolled steel plate with black scale (JIS G 3131) was immersed, and the time required for removing black scale and rust on the surface was measured. Table 1 shows the results.
【００３７】比較例１ 実施例１〜３と同じ条件で実験を行った。ただし酸洗促
進剤は用いていない。その結果を表１に示す。Comparative Example 1 An experiment was performed under the same conditions as in Examples 1 to 3. However, no pickling accelerator was used. Table 1 shows the results.
【００３８】[0038]
【表１】 [Table 1]
【００３９】実施例４〜６ １ｌ中に硫酸１００ｇと第１鉄イオン５０ｇと腐食抑制
剤イビットＮｏ．６００ＬＴ２（朝日化学工業株式会社
製）１ｇとを含む酸洗液に、本発明の酸洗促進剤を２ｇ
添加し、この液を９５℃まで加温した後、黒皮付きの熱
延鋼板（ＪＩＳＧ ３１３１）を浸漬し、表面の黒皮、
錆の除去に要する時間を測定した。その結果を表２に示
す。Examples 4 to 6 100 g of sulfuric acid, 50 g of ferrous ion and corrosion inhibitor Ibit No. 2 g of the pickling accelerator of the present invention in a pickling solution containing 1 g of 600LT2 (manufactured by Asahi Chemical Industry Co., Ltd.).
After the solution was heated to 95 ° C., a hot-rolled steel sheet with black scale (JISG 3131) was immersed, and the black scale on the surface was removed.
The time required for rust removal was measured. Table 2 shows the results.
【００４０】比較例２ 実施例４〜６と同じ条件で実験を行った。ただし、酸洗
促進剤は用いていない。その結果を表２に示す。Comparative Example 2 An experiment was performed under the same conditions as in Examples 4 to 6. However, no pickling accelerator was used. Table 2 shows the results.
【００４１】[0041]
【表２】 [Table 2]
【００４２】実施例７〜９ １ｌ中に塩酸５０ｇと第１鉄イオン５０ｇと腐食抑制剤
イビットＮｏ．７１０Ｎ（朝日化学工業株式会社製）１
ｇとを含む酸洗液に、本発明の酸洗促進剤を２ｇ添加
し、この液を９０℃まで加温した後、黒皮付きの熱延鋼
板（ＪＩＳ Ｇ３１３１）を浸漬し、表面の黒皮、錆の
除去に要する時間を測定した。その結果を表３に示す。Examples 7-9 50 g of hydrochloric acid, 50 g of ferrous ion, and corrosion inhibitor IBIT No. 710N (made by Asahi Chemical Industry Co., Ltd.) 1
g of the acid pickling accelerator of the present invention was added to the pickling solution containing g, and the solution was heated to 90 ° C., and then a hot-rolled steel sheet with black scale (JIS G3131) was immersed in the pickling solution to obtain a blackened surface. The time required to remove the skin and rust was measured. Table 3 shows the results.
【００４３】比較例３ 実施例７と同じ条件で実験を行った。ただし酸洗促進剤
は用いていない。その結果を表３に示す。Comparative Example 3 An experiment was performed under the same conditions as in Example 7. However, no pickling accelerator was used. Table 3 shows the results.
【００４４】[0044]
【表３】 [Table 3]
【００４５】実施例１０〜１２ １ｌ中に塩酸１００ｇと第１鉄イオン５０ｇと腐食抑制
剤イビットＮｏ．７００Ａ（朝日化学工業株式会社製）
１ｇとを含む酸洗液に、本発明の酸洗促進剤を２ｇ添加
し、この液を３０℃まで加温した後、黒皮付きの熱延鋼
板（ＪＩＳ Ｇ３１３１）を浸漬し、表面の黒皮、錆の
除去に要する時間を測定した。その結果を表４に示す。Examples 10 to 12 In one liter, 100 g of hydrochloric acid, 50 g of ferrous ion and the corrosion inhibitor Ibit No. 700A (made by Asahi Chemical Industry Co., Ltd.)
2 g of the pickling accelerator of the present invention was added to the pickling solution containing 1 g of the solution, and the solution was heated to 30 ° C., and then a hot-rolled steel plate with black scale (JIS G 3131) was immersed in the solution to obtain a black surface. The time required to remove the skin and rust was measured. Table 4 shows the results.
【００４６】比較例４ 実施例７と同じ条件で実験を行った。ただし、酸洗促進
剤は用いていない。その結果を表４に示す。Comparative Example 4 An experiment was performed under the same conditions as in Example 7. However, no pickling accelerator was used. Table 4 shows the results.
【００４７】[0047]
【表４】 [Table 4]
【００４８】実施例１３ １ｌ中にリン酸５０ｇと腐食抑制剤イビットＮｏ．６０
０Ｌ（朝日化学工業株式会社製）１ｇとを含む酸洗液
に、本発明の酸洗促進剤を２ｇ添加し、この液を６０℃
まで加温した後、黒皮付きの熱延鋼板（ＪＩＳ Ｇ ３
１３１）を浸漬し、表面の黒皮、錆の除去に要する時間
を測定した。その結果を表５に示す。Example 13 50 g of phosphoric acid and the corrosion inhibitor Ibit No. 60
2 g of the pickling accelerator of the present invention was added to a pickling solution containing 1 g of 0 L (manufactured by Asahi Chemical Industry Co., Ltd.).
And then heat-rolled steel plate with black scale (JIS G3
131) was immersed, and the time required to remove black scale and rust on the surface was measured. Table 5 shows the results.
【００４９】比較例５ 実施例１３と同じ条件で実験を行った。ただし酸洗促進
剤は用いていない。その結果を表５に示す。Comparative Example 5 An experiment was performed under the same conditions as in Example 13. However, no pickling accelerator was used. Table 5 shows the results.
【００５０】実施例１４ １ｌ中にスルファミン酸５０ｇと腐食抑制剤イビットＮ
ｏ．３ＨＡ（朝日化学工業株式会社製）５ｇとを含む酸
洗液に、本発明の酸洗促進剤を２ｇ添加し、この液を６
０℃まで加温した後、黒皮付きの熱延鋼板（ＪＩＳ Ｇ
３１３１）を浸漬し、表面の黒皮、錆の除去に要する
時間を測定した。その結果を表５に示す。Example 14 50 g of sulfamic acid and the corrosion inhibitor Ivit N in 1 l
o. 2 g of the pickling accelerator of the present invention was added to a pickling solution containing 5 g of 3HA (manufactured by Asahi Chemical Industry Co., Ltd.), and
After heating to 0 ° C, hot-rolled steel sheet with black scale (JIS G
3131) was immersed, and the time required to remove black scale and rust on the surface was measured. Table 5 shows the results.
【００５１】比較例６ 実施例１４と同じ条件で実験を行った。ただし酸洗促進
剤は用いていない。その結果を表５に示す。Comparative Example 6 An experiment was performed under the same conditions as in Example 14. However, no pickling accelerator was used. Table 5 shows the results.
【００５２】実施例１５ １ｌ中にクエン酸モノアンモニウム３０ｇと腐食抑制剤
イビットＮｏ．３０Ａ（朝日化学工業株式会社製）３ｇ
とを含む酸洗液に、本発明の酸洗促進剤を２ｇ添加し、
この液を９０℃まで加温した後、黒皮付きの熱延鋼板
（ＪＩＳ Ｇ ３１３１）を浸漬し、表面の黒皮、錆の
除去に要する時間を測定した。その結果を表５に示す。Example 15 30 g of monoammonium citrate and Ibit No. 30g (Asahi Chemical Industry Co., Ltd.) 3g
2 g of the pickling accelerator of the present invention is added to a pickling solution containing
After the solution was heated to 90 ° C., a hot-rolled steel sheet with black scale (JIS G 3131) was immersed, and the time required to remove black scale and rust on the surface was measured. Table 5 shows the results.
【００５３】比較例７ 実施例１５と同じ条件で実験を行った。ただし、酸洗促
進剤は用いていない。その結果を表５に示す。Comparative Example 7 An experiment was performed under the same conditions as in Example 15. However, no pickling accelerator was used. Table 5 shows the results.
【００５４】実施例１６ １ｌ中にヒドロキシ酢酸１００ｇを含む液と１ｌ中にギ
酸１００ｇを含む液を混ぜた液１ｌに腐食抑制剤イビッ
トＮｏ．３０Ａ（朝日化学工業株式会社製）３ｇを加え
た酸洗液に、本発明の酸洗促進剤を２ｇ添加し、この液
を９０℃まで加温した後、黒皮付きの熱延鋼板（ＪＩＳ
Ｇ ３１３１）を浸漬し、表面の黒皮、錆の除去に要
する時間を測定した。その結果を表５に示す。Example 16 A solution containing 100 g of hydroxyacetic acid in 1 liter and a solution containing 100 g of formic acid in 1 liter was mixed with 1 liter of the solution of corrosion inhibitor Ibit No. To a pickling solution to which 3 g of 30A (manufactured by Asahi Chemical Industry Co., Ltd.) was added, 2 g of the pickling accelerator of the present invention was added, the solution was heated to 90 ° C., and then a hot-rolled steel sheet with black scale (JIS)
G 3131) was immersed, and the time required to remove black scale and rust on the surface was measured. Table 5 shows the results.
【００５５】比較例８ 実施例１６と同じ条件で実験を行った。ただし、酸洗促
進剤は用いていない。その結果を表５に示す。Comparative Example 8 An experiment was performed under the same conditions as in Example 16. However, no pickling accelerator was used. Table 5 shows the results.
【００５６】[0056]
【表５】 [Table 5]
【００５７】実施例１７ １ｌ中に硫酸１００ｇと第１鉄イオン５０ｇと腐食抑制
剤イビットＮｏ．Ｓ６００Ａ（朝日化学工業株式会社
製）１ｇとを含む酸洗液に、本発明の酸洗促進剤を２ｇ
添加し、この液を６０℃まで加温した後、上記実施例１
〜１６で黒皮を除去した熱延鋼板（ＪＩＳ Ｇ ３１３
１）を浸漬し、腐食量を求めた。ただし腐食量は浸漬前
後の鋼板の重量差を鋼板の表面積と浸漬時間で除した量
である。その結果を表６に示す。Example 17 100 g of sulfuric acid, 50 g of ferrous ion, and corrosion inhibitor IBIT No. 2 g of the pickling accelerator of the present invention in a pickling solution containing 1 g of S600A (manufactured by Asahi Chemical Industry Co., Ltd.).
After heating the solution to 60 ° C.,
Hot rolled steel sheet (JIS G 313)
1) was immersed, and the amount of corrosion was determined. However, the amount of corrosion is the amount obtained by dividing the weight difference between the steel sheet before and after immersion by the surface area of the steel sheet and the immersion time. Table 6 shows the results.
【００５８】比較例９，１０ 実施例１と同じ条件で実験を行った。ただし酸洗促進剤
は用いず、または本発明の酸洗促進剤の代わりにチオ硫
酸アンモニウムを用いた。その結果を表６に示す。Comparative Examples 9 and 10 Experiments were performed under the same conditions as in Example 1. However, no pickling accelerator was used, or ammonium thiosulfate was used instead of the pickling accelerator of the present invention. Table 6 shows the results.
【００５９】実施例１８ 腐食抑制剤をイビットＮｏ．６００ＬＴＳ（朝日化学工
業株式会社製）にしたこと、および酸洗液の温度を９５
℃にしたこと以外は、実施例１７と同じ条件で実験を行
った。その結果を表６に示す。Example 18 The corrosion inhibitor was Ibit No. 600 LTS (made by Asahi Chemical Industry Co., Ltd.) and the temperature of the pickling solution was set to 95
The experiment was performed under the same conditions as in Example 17 except that the temperature was changed to ° C. Table 6 shows the results.
【００６０】比較例１１ 実施例１と同じ条件で実験を行った。ただし酸洗促進剤
は用いていない。その結果を表６に示す。Comparative Example 11 An experiment was performed under the same conditions as in Example 1. However, no pickling accelerator was used. Table 6 shows the results.
【００６１】実施例１９ １ｌ中に塩酸１００ｇと第１鉄イオン５０ｇと腐食抑制
剤イビットＮｏ．７００Ａ（朝日化学工業株式会社製）
１ｇとを含む酸洗液に、本発明の酸洗促進剤を２ｇ添加
し、この液を３０℃まで加温した後、上記実施例１〜１
６で黒皮を除去した熱延鋼板（ＪＩＳ Ｇ ３１３１）
を浸漬し、腐食量を求めた。その結果を表６に示す。Example 19 100 g of hydrochloric acid, 50 g of ferrous ion and corrosion inhibitor IBIT No. 700A (made by Asahi Chemical Industry Co., Ltd.)
2 g of the pickling accelerator of the present invention was added to the pickling solution containing 1 g of the solution, and the solution was heated to 30 ° C.
Hot rolled steel sheet from which black scale has been removed in Step 6 (JIS G 3131)
Was immersed to determine the amount of corrosion. Table 6 shows the results.
【００６２】比較例１２ 実施例１９と同じ条件で実験を行った。ただし、酸洗促
進剤は用いていない。その結果を表６に示す。Comparative Example 12 An experiment was performed under the same conditions as in Example 19. However, no pickling accelerator was used. Table 6 shows the results.
【００６３】[0063]
【表６】 [Table 6]
【００６４】実施例２０〜２８および比較例１３ １ｌ中に硫酸１００ｇと第１鉄イオン５０ｇと腐食抑制
剤イビットＮｏ．Ｓ６００Ａ（朝日化学工業株式会社
製）１ｇとを含む酸洗液に、本発明の酸洗促進剤の１種
であるエチレングリコールジチオグリコレートを０ｍｇ
〜１０，０００ｍｇの範囲で添加し、この液を６０℃ま
で加温した後、黒皮付き熱延鋼板を浸漬表面の黒皮およ
び錆の除去に要する時間を測定した。この結果を表７に
示す。Examples 20 to 28 and Comparative Example 13 In one liter, 100 g of sulfuric acid, 50 g of ferrous ion and the corrosion inhibitor Ibit No. S600A (manufactured by Asahi Chemical Industry Co., Ltd.) in an acid pickling solution containing 1 g of ethylene glycol dithioglycolate, one of the pickling accelerators of the present invention.
After the solution was heated to 60 ° C., the time required for removing the scale and rust on the immersed surface of the hot-rolled steel sheet with the scale was measured. Table 7 shows the results.
【００６５】[0065]
【表７】 [Table 7]
【００６６】実施例２９〜３５および比較例１４ １ｌ中に塩酸１００ｇと第１鉄イオン５０ｇと腐食抑制
剤イビットＮｏ．７００Ａ（朝日化学工業株式会社製）
１ｇとを含む酸洗液に、本発明の酸洗促進剤の１種であ
るエチレングリコールジチオグリコレートを０ｍｇ〜１
０，０００ｍｇの範囲で添加し、この液を６０℃まで加
温した後黒皮付き熱延鋼板を浸漬し表面の黒皮および錆
の除去に要する時間を測定した。この結果を表８に示
す。Examples 29 to 35 and Comparative Example 14 100 g of hydrochloric acid, 50 g of ferrous ion and corrosion inhibitor IBIT No. 700A (made by Asahi Chemical Industry Co., Ltd.)
1 g of ethylene glycol dithioglycolate, one of the pickling accelerators of the present invention, in an amount of 0 mg to 1 g.
After the solution was heated to 60 ° C., the hot-rolled steel sheet with black scale was immersed in the solution, and the time required to remove black scale and rust on the surface was measured. Table 8 shows the results.
【００６７】[0067]
【表８】 [Table 8]
【００６８】実施例３６ １ｌ中に硫酸２５０ｇと第１鉄イオン６０ｇと腐食抑制
剤イビットＮｏ．６００ＬＴ２（朝日化学工業株式会社
製）１ｇとを含む酸洗液に、本発明の酸洗促進剤を１ｇ
添加し、この液を９５℃まで加温した後、２時間の間に
有毒ガスの発生はなかった。Example 36 250 g of sulfuric acid, 60 g of ferrous ions and corrosion inhibitor Ibit No. 1 g of the pickling accelerator of the present invention in a pickling solution containing 1 g of 600LT2 (manufactured by Asahi Chemical Industry Co., Ltd.).
After adding and warming the solution to 95 ° C., no toxic gas was generated during 2 hours.
【００６９】比較例１５ 実施例３６と同じ酸洗液に、従来の酸洗促進剤であるチ
オ硫酸アンモニウムを１ｇ添加し、この液を９５℃まで
加温した後、２時間の間に硫化水素ガスが５０ｍｌ発生
した。COMPARATIVE EXAMPLE 15 1 g of ammonium thiosulfate, a conventional pickling accelerator, was added to the same pickling solution as in Example 36, and the solution was heated to 95 ° C., and then hydrogen sulfide gas was added for 2 hours. Occurred in 50 ml.
【００７０】実施例３７，３８ 本発明の酸洗促進剤の１種であるエチレングリコールジ
チオグリコレートを０．１％含んだ２５％硫酸から成る
酸洗液組成物を製造し、ただちにまたは１週間経過後、
この組成物を水で５倍に希釈し、６０℃に加温した後、
黒皮付き熱延鋼板を浸漬し表面の黒皮、錆の除去に要す
る時間を測定した。その結果を表９に示す。Examples 37 and 38 A pickling liquid composition comprising 25% sulfuric acid containing 0.1% of ethylene glycol dithioglycolate, one of the pickling accelerators of the present invention, was prepared and immediately or for one week. After a while,
After diluting this composition 5 times with water and warming to 60 ° C,
A hot-rolled steel sheet with a black scale was immersed in it, and the time required for removing the black scale and rust on the surface was measured. Table 9 shows the results.
【００７１】比較例１６ ２５％硫酸を水で５倍希釈し、６０℃加温した後、黒皮
付き熱延鋼板を浸漬し表面の黒皮、錆の除去に要する時
間を測定した。その結果を表９に示す。Comparative Example 16 After 25% sulfuric acid was diluted 5-fold with water and heated at 60 ° C., a hot-rolled steel sheet with a black scale was immersed in it, and the time required for removing black scale and rust on the surface was measured. Table 9 shows the results.
【００７２】実施例３９，４０ 本発明の酸洗促進剤の１種であるエチレングリコールジ
チオグリコレート１％とクエン酸９９％から成る酸洗液
組成物を製造し、ただちにまたは１週間経過後、この組
成物を水で２０倍に希釈し、９０℃に加温した後、黒皮
付き熱延鋼板を浸漬し表面の黒皮、錆の除去に要する時
間を測定した。その結果を表９に示す。Examples 39 and 40 A pickling solution composition comprising 1% of ethylene glycol dithioglycolate and 99% of citric acid, one of the pickling accelerators of the present invention, was prepared, and immediately or after one week, This composition was diluted 20-fold with water and heated to 90 ° C., and then a hot-rolled steel sheet with a black scale was immersed to measure the time required for removing black scale and rust on the surface. Table 9 shows the results.
【００７３】比較例１７ 純クエン酸を水で２０倍に希釈し、９０℃加温した後、
黒皮付き熱延鋼板を浸漬し表面の黒皮、錆の除去に要す
る時間を測定した。その結果を表９に示す。Comparative Example 17 Pure citric acid was diluted 20-fold with water and heated at 90 ° C.
A hot-rolled steel sheet with a black scale was immersed in it, and the time required for removing the black scale and rust on the surface was measured. Table 9 shows the results.
【００７４】実施例４１，４２ 本発明の酸洗促進剤の１種であるエチレングリコールジ
チオグリコレート２％とヒドロキシ酢酸４９％およびギ
酸４９％から成る酸洗液組成物を製造し、ただちにまた
は１週間経過後、この組成物を水で２０倍に希釈し、９
０℃に加温した後、黒皮付き熱延鋼板を浸漬し表面の黒
皮、錆の除去に要する時間を測定した。その結果を表９
に示す。Examples 41 and 42 A pickling liquid composition comprising 2% of ethylene glycol dithioglycolate, one of the pickling accelerators according to the present invention, 49% of hydroxyacetic acid and 49% of formic acid was prepared, and immediately or immediately. After a week, the composition was diluted 20 times with water,
After heating to 0 ° C., the hot-rolled steel sheet with black scale was immersed, and the time required to remove black scale and rust on the surface was measured. Table 9 shows the results.
Shown in
【００７５】比較例１８ ヒドロキシ酢酸５０％およびギ酸５０％の混合物を水で
２０倍に希釈し、９０℃加温した後、黒皮付き熱延鋼板
を浸漬し表面の黒皮、錆の除去に要する時間を測定し
た。その結果を表９に示す。Comparative Example 18 A mixture of 50% hydroxyacetic acid and 50% formic acid was diluted 20-fold with water, heated at 90 ° C., and then immersed in a hot-rolled steel sheet with black scale to remove black scale and rust on the surface. The time required was measured. Table 9 shows the results.
【００７６】[0076]
【表９】 [Table 9]
【００７７】実施例４３，４４ １ｌ中に塩酸５０ｇを含む酸洗液に、本発明の酸洗促進
剤の１種であるエチレングリコールジチオグリコレート
を１ｇ添加し、この液を６０℃に加温した後、銅および
真ちゅうの酸洗を行い、表面の黒皮、錆の除去に要した
時間を測定した。この結果を表１０に示す。Examples 43 and 44 1 g of ethylene glycol dithioglycolate, one of the pickling accelerators of the present invention, was added to a pickling solution containing 50 g of hydrochloric acid in 1 liter, and the solution was heated to 60 ° C. After that, the copper and brass were pickled, and the time required for removing black scale and rust on the surface was measured. Table 10 shows the results.
【００７８】比較例１９，２０ 実施例４０，４１と同じ条件で実験を行った。ただし、
酸洗促進剤は用いていない。その結果を表１０に示す。Comparative Examples 19 and 20 Experiments were performed under the same conditions as in Examples 40 and 41. However,
No pickling accelerator was used. Table 10 shows the results.
【００７９】[0079]
【表１０】 [Table 10]
【００８０】[0080]
【発明の効果】実施例１〜３と比較例１および表１から
明らかなように、酸洗液として１００ｇ／ｌ硫酸＋５０
ｇ／ｌＦｅ2+を用い６０℃の酸洗条件では、本発明の酸
洗促進剤の２ｇ／ｌの添加は、金属の酸洗促進に顕著な
効果がある。As is clear from Examples 1 to 3, Comparative Example 1 and Table 1, 100 g / l sulfuric acid + 50 as a pickling solution was used.
Under the pickling condition of 60 ° C. using g / l Fe 2+ , the addition of 2 g / l of the pickling accelerator of the present invention has a remarkable effect on accelerating the pickling of metal.
【００８１】同様に、実施例４〜１６と比較例２〜８お
よび表２〜表５から、塩酸、リン酸、スルファミン酸な
どの無機酸およびクエン酸、ギ酸、ヒドロキシ酢酸など
の有機酸ならびにこれらの酸の混酸にも、本発明の酸洗
促進剤の２ｇ／ｌの添加は、金属の酸洗促進に顕著な効
果がある。Similarly, from Examples 4 to 16, Comparative Examples 2 to 8 and Tables 2 to 5, inorganic acids such as hydrochloric acid, phosphoric acid and sulfamic acid and organic acids such as citric acid, formic acid and hydroxyacetic acid, and Addition of 2 g / l of the pickling accelerator of the present invention to the mixed acid of the above acids has a remarkable effect on accelerating the pickling of the metal.
【００８２】また、実施例１７〜１９と比較例９〜１２
および表６から明らかなように、本発明の酸洗促進剤の
２ｇ／ｌの添加は、従来から使用されている腐食抑制剤
の金属の母材の腐食を抑える効果に対し悪影響を与えな
い効果がある。Examples 17 to 19 and Comparative Examples 9 to 12
As is clear from Table 6 and Table 6, the addition of 2 g / l of the pickling accelerator of the present invention has the effect of not adversely affecting the effect of the conventionally used corrosion inhibitor on inhibiting the corrosion of the metal base material. There is.
【００８３】また、実施例２０〜３５と比較例１３，１
４および表７，表８から明らかなように酸洗液に対する
本発明の酸洗促進剤の効果は、その添加量が１０ｍｇ／
ｌ以上で効果がある。また、５０ｍｇ／ｌ以上で顕著な
効果があり、４，０００ｍｇ／ｌ以上にしてもその効果
はほとんど変わらない。Further, Examples 20 to 35 and Comparative Examples 13 and 1
4 and Tables 7 and 8, the effect of the pickling accelerator of the present invention on the pickling solution was as follows.
1 or more is effective. Further, there is a remarkable effect at 50 mg / l or more, and the effect is hardly changed even at 4,000 mg / l or more.
【００８４】また実施例３６と比較例１５より明らかな
ように本発明の酸洗促進剤は、従来の酸洗促進剤のよう
に酸洗期間中に有毒ガスの発生がない。Further, as is clear from Example 36 and Comparative Example 15, the pickling accelerator of the present invention does not generate toxic gas during the pickling period unlike the conventional pickling accelerator.
【００８５】また実施例３７，３８と比較例１６および
表９から明らかなように無機酸および／または有機酸の
少なくとも１種の水溶液であって、酸の含有量が１〜５
０％であるものに本発明の酸洗促進剤を０．００１％以
上添加した酸洗組成物は、組成物製造後も安定であり、
これを水で所要の濃度に希釈して使っても顕著な効果が
ある。Further, as is clear from Examples 37 and 38, Comparative Example 16 and Table 9, at least one aqueous solution of an inorganic acid and / or an organic acid, wherein the acid content is 1 to 5
A pickling composition containing 0.001% or more of the acid pickling accelerator of the present invention to 0% is stable even after the production of the composition,
This can be used to dilute it with water to the required concentration, which has a remarkable effect.
【００８６】また実施例３９〜４２と比較例１７，１８
および表９から明らかなように、有機酸の少なくとも１
種から成る酸の含有量が９９．９９％未満であるものに
本発明の酸洗促進剤を０．０１％以上添加した酸洗組成
物は、組成物製造後も安定であり、これを水で所要の濃
度に希釈して使っても顕著な効果がある。Examples 39 to 42 and Comparative Examples 17 and 18
And from Table 9 that at least one of the organic acids
The pickling composition containing less than 99.99% of the acid composed of the seed and the acid pickling accelerator of the present invention added in an amount of 0.01% or more is stable even after the preparation of the composition, and There is a remarkable effect even when used after diluting to the required concentration.
【００８７】また前記各実施例と比較例および実施例４
３，４４と比較例１９，２０および表１０より明らかな
ように、本促進剤を酸洗液に添加したものは、銅および
銅合金である真ちゅうならびに圧延鋼の酸洗に用いて顕
著な効果がある。この効果は他の鉄合金についてもいえ
る。Further, each of the above embodiments, the comparative example, and the embodiment 4
3, 44 and Comparative Examples 19 and 20 and Table 10, the addition of the present accelerator to the pickling solution has a remarkable effect on the pickling of copper and copper alloy brass and rolled steel. There is. This effect can be applied to other iron alloys.
【００８８】以上のように本発明によれば、本発明の酸
洗促進剤および酸洗促進組成物ならびに酸洗促進方法
は、従来から使用されている腐食抑制剤による金属の母
材の腐食を抑制する効果に悪影響をおよぼすことなく表
面酸化物皮膜、汚染物等の除去に必要な時間を大幅に短
縮できる。しかも、本発明の酸洗促進剤および酸洗促進
剤を含んだ酸洗液組成物ならびに酸洗促進方法は、有害
ガスが発生しないため新たな除外装置などの設備などを
必要としないため工業的価値が大きい。As described above, according to the present invention, the acid pickling accelerator, the acid pickling accelerating composition and the acid pickling accelerating method of the present invention prevent the corrosion of a metal base material by a conventionally used corrosion inhibitor. The time required for removing the surface oxide film, contaminants, and the like can be significantly reduced without adversely affecting the suppression effect. Moreover, the pickling accelerator composition and the pickling solution composition containing the pickling accelerator and the pickling accelerating method of the present invention do not require harmful gases and do not require equipment such as a new elimination device. Great value.
Claims (9)
表される化合物の少なくとも１種を無機酸および／また
は有機酸の水溶液に添加することによって金属の酸洗速
度を促進することを特徴とする酸洗促進剤。 【化１】 ＨＳＲ1−ＣＯＯ−Ｒ2−ＯＯＣ−Ｒ3ＳＨ Ｒ1，Ｒ2，Ｒ3 は、炭素１〜６のアルキル基を示し、そ
れぞれ同一であってもよく異なっていてもよい。In the step of pickling a metal, at least one of the compounds represented by the following formula 1 is added to an aqueous solution of an inorganic acid and / or an organic acid to accelerate the pickling rate of the metal. A characteristic pickling accelerator. Embedded image HSR 1 —COO—R 2 —OOC—R 3 SH R 1 , R 2 and R 3 each represent an alkyl group having 1 to 6 carbon atoms, and may be the same or different.
もしくは１，４−ブタンジオールジチオプロピオネート
またはこれらの混合物を無機酸および／または有機酸の
水溶液に添加することによって金属の酸洗速度を促進す
ることを特徴する請求項１記載の酸洗促進剤。2. Enhancing the pickling rate of a metal by adding ethylene glycol dithioglycolate or 1,4-butanediol dithiopropionate or a mixture thereof to an aqueous solution of an inorganic acid and / or an organic acid. The pickling accelerator according to claim 1, characterized in that:
も１種の水溶液から成り、酸の含有量が１〜５０％、下
記の化２で表される化合物の少なくとも１種の含有量が
０．００１％以上であることを特徴とする酸洗促進剤を
含んだ酸洗液組成物。 【化２】 ＨＳＲ1−ＣＯＯ−Ｒ2−ＯＯＣ−Ｒ3ＳＨ Ｒ1，Ｒ2，Ｒ3 は、炭素数１〜６のアルキル基を示し、
それぞれ同一であってもよく異なっていてもよい。3. An aqueous solution of at least one kind of an inorganic acid and / or an organic acid, wherein the content of the acid is 1 to 50%, and the content of at least one kind of the compound represented by the following chemical formula 2 is 0. A pickling liquid composition containing a pickling accelerator characterized by being at least 001%. Embedded image HSR 1 —COO—R 2 —OOC—R 3 SH R 1 , R 2 and R 3 each represent an alkyl group having 1 to 6 carbon atoms;
Each may be the same or different.
少なくとも１種から成る酸の含有量が９９．９９％未満
と、下記の化３で表される化合物の少なくとも１種の含
有量が０．０１％以上であることを特徴とする酸洗促進
剤を含んだ酸洗液組成物。 【化３】 ＨＳＲ1−ＣＯＯ−Ｒ2−ＯＯＣ−Ｒ3ＳＨ Ｒ1，Ｒ2，Ｒ3 は、炭素数１〜６のアルキル基を示し、
それぞれ同一であってもよく異なっていてもよい。4. When the content of an acid composed of at least one of sulfamic acid and / or an organic acid is less than 99.99%, the content of at least one compound represented by the following chemical formula 3 is 0.01%. % Or more, a pickling liquid composition containing a pickling accelerator. Embedded image HSR 1 —COO—R 2 —OOC—R 3 SH R 1 , R 2 and R 3 each represent an alkyl group having 1 to 6 carbon atoms;
Each may be the same or different.
ミン酸、フッ酸または硝酸であり、有機酸が酢酸、シュ
ウ酸、クエン酸、ギ酸、酒石酸、リンゴ酸、ヒドロキシ
酸またはグルコン酸であることを特徴とする請求項３ま
たは請求項４記載の酸洗促進剤を含んだ酸洗組成物。5. The inorganic acid is sulfuric acid, hydrochloric acid, phosphoric acid, sulfamic acid, hydrofluoric acid or nitric acid, and the organic acid is acetic acid, oxalic acid, citric acid, formic acid, tartaric acid, malic acid, hydroxy acid or gluconic acid. A pickling composition containing the pickling accelerator according to claim 3 or 4.
ら成る酸洗液１ｌに、下記の化４で表される化合物の少
なくとも１種類を１０ｍｇ以上添加した液を用いること
を特徴とする金属の酸洗促進方法。 【化４】 ＨＳＲ1−ＣＯＯ−Ｒ2−ＯＯＣ−Ｒ3ＳＨ Ｒ1，Ｒ2，Ｒ3 は、炭素数１〜６のアルキル基を示し、
それぞれ同一であってもよく異なっていてもよい。6. A metal pickling solution comprising at least 10 mg of at least one compound represented by the following chemical formula (4) added to 1 liter of an aqueous solution of an inorganic acid and / or an organic acid. Pickling promotion method. Embedded image HSR 1 —COO—R 2 —OOC—R 3 SH R 1 , R 2 and R 3 each represent an alkyl group having 1 to 6 carbon atoms;
Each may be the same or different.
ら成る酸洗液１ｌに、前記化１で表される化合物の少な
くとも１種類を５０ｍｇ以上４，０００ｍｇ以下添加し
た液を用いることを特徴とする請求項６記載の金属の酸
洗促進方法。7. A solution obtained by adding at least one kind of the compound represented by Chemical Formula 1 to 50 mg or more and 4,000 mg or less to 1 liter of an pickling solution comprising an aqueous solution of an inorganic acid and / or an organic acid. The method for accelerating pickling of metals according to claim 6.
ミン酸、フッ酸または硝酸であり、有機酸が酢酸、シュ
ウ酸、クエン酸、ギ酸、酒石酸、リンゴ酸、ヒドロキシ
酸またはグルコン酸であることを特徴とする請求項６記
載の金属の酸洗促進方法。8. The inorganic acid is sulfuric acid, hydrochloric acid, phosphoric acid, sulfamic acid, hydrofluoric acid or nitric acid, and the organic acid is acetic acid, oxalic acid, citric acid, formic acid, tartaric acid, malic acid, hydroxy acid or gluconic acid. 7. The method for accelerating pickling of metals according to claim 6, wherein:
ら成る酸洗液１ｌに、前記化１で表される化合物の少な
くとも１種類を１０ｍｇ以上添加した液を用いることを
特徴とする請求項６記載の鉄鋼、銅およびこれらの金属
の合金の酸洗方法。9. A solution prepared by adding at least 10 mg of at least one kind of the compound represented by the formula (1) to 1 liter of an acid washing solution comprising an aqueous solution of an inorganic acid and / or an organic acid. A method for pickling steel, copper and alloys of these metals as described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05522392A JP3160051B2 (en) | 1992-03-13 | 1992-03-13 | Pickling accelerator, pickling liquid composition containing pickling accelerator, and method for promoting pickling of metal using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05522392A JP3160051B2 (en) | 1992-03-13 | 1992-03-13 | Pickling accelerator, pickling liquid composition containing pickling accelerator, and method for promoting pickling of metal using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05255874A JPH05255874A (en) | 1993-10-05 |
| JP3160051B2 true JP3160051B2 (en) | 2001-04-23 |
Family
ID=12992614
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05522392A Expired - Fee Related JP3160051B2 (en) | 1992-03-13 | 1992-03-13 | Pickling accelerator, pickling liquid composition containing pickling accelerator, and method for promoting pickling of metal using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3160051B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6426390B1 (en) | 1999-06-11 | 2002-07-30 | Dow Global Technology Inc. | Hydrogenated block copolymer compositions |
| US6815475B2 (en) | 1999-06-11 | 2004-11-09 | Dow Global Technologies Inc. | Compositions comprising hydrogenated block copolymers and end-use applications thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001316860A (en) * | 2000-05-11 | 2001-11-16 | Sumitomo Metal Ind Ltd | Attractive electrogalvanized steel sheet and manufacturing method |
| JP2005036288A (en) * | 2003-07-16 | 2005-02-10 | Asahi Denka Kogyo Kk | Pickling bath composition for metal surface |
| KR20140095266A (en) | 2013-01-24 | 2014-08-01 | 한국원자력연구원 | Chelate free chemical decontamination reagent for removal of the dense radioactive oxide layer on the metal surface and chemical decontamination method using the same |
| KR101601201B1 (en) * | 2015-04-15 | 2016-03-09 | 한국원자력연구원 | Chelate free chemical decontamination reagent for removal of the dense radioactive oxide layer on the metal surface and chemical decontamination method using the same |
| US10443135B1 (en) * | 2018-05-11 | 2019-10-15 | Macdermid Enthone Inc. | Near neutral pH pickle on multi-metals |
| KR102246676B1 (en) | 2018-12-27 | 2021-04-30 | 남동화학(주) | Picking solution for hot dip galvanizing process and method of manufacturing the same |
-
1992
- 1992-03-13 JP JP05522392A patent/JP3160051B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6426390B1 (en) | 1999-06-11 | 2002-07-30 | Dow Global Technology Inc. | Hydrogenated block copolymer compositions |
| US6815475B2 (en) | 1999-06-11 | 2004-11-09 | Dow Global Technologies Inc. | Compositions comprising hydrogenated block copolymers and end-use applications thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05255874A (en) | 1993-10-05 |
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